JP2012066950A - Method for producing carbon material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a means to supply a carbon material of stable quality, in a method for producing a carbon material, by minimizing distortion and collapse of the structure of the resulting carbon material in the production process.SOLUTION: A method for producing a carbon material includes: a step (first step) of preparing as a template a porous metal complex including a three-dimensional porous skeleton structure of a metal complex represented by the formula: M(OH)R (wherein M is a central metal, and R is an organic ligand); a step (second step) of bringing the porous metal complex into contact with an organic compound to thereby form the coating film of the organic compound on the surface of the porous metal complex; and a step (third step) of heating the metal complex with the coating film of the organic compound formed on the surface to thereby polymerize and carbonize the organic compound.

Description

  The present invention relates to a method for producing a carbon material.

  In recent years, carbon materials have attracted a great deal of attention as energy storage materials such as negative electrode active materials for lithium ion batteries and hydrogen storage materials for fuel cells.

  Here, for example, graphite, which is most often used as a negative electrode active material of a lithium ion secondary battery, causes expansion / contraction due to insertion / desorption of lithium, or a reaction of an electrolyte proceeds on the surface of the negative electrode active material. As a result, there is a problem of reducing the battery life. From the viewpoint of improving the capacity characteristics and output characteristics of the battery, it is considered necessary to design and synthesize the structure of the carbon material at the molecular level. Based on such an idea, for example, a method for producing a carbon material using a metal coordination polymer compound (porous metal complex) as a template has been disclosed (see Patent Document 1).

JP 2009-143786 A

  In the production of a carbon material by using a porous metal complex as disclosed in Patent Document 1 as a template, the template can be removed by heating. For this reason, there exists an advantage that a carbon material can be manufactured cheaply.

  And this inventor also tried to manufacture a carbon material using a porous metal complex as a casting_mold | template like the method of patent document 1. FIG. However, it has been found that the structure of the carbon material obtained by this method may be distorted or collapsed during the manufacturing process. Thus, when the structure of the carbon material is distorted or collapsed, it is a very big problem when producing a stable quality carbon material in large quantities.

  An object of the present invention is to provide means for suppressing the distortion and collapse in the manufacturing process of the structure of the obtained carbon material to the minimum and enabling the supply of a stable quality carbon material in the carbon material manufacturing method. And

  The inventors of the present invention have made extensive studies in view of the above problems. In the process, when a porous metal complex containing a hydroxy group (—OH group) is used as a template, the inventors have found that the above problem can be solved, and have completed the present invention.

  That is, according to one aspect of the present invention, there is provided a method for producing a carbon material, which is a metal represented by M (OH) R (wherein M is a central metal and R is an organic ligand). A step of preparing a porous metal complex including a three-dimensional porous skeleton structure of the complex as a template, contacting the porous metal complex with an organic compound, and coating the organic compound on the surface of the porous metal complex And a method of heating the metal complex having a coating film of the organic compound formed on the surface thereof to polymerize and carbonize the organic compound.

  According to the present invention, the water resistance of the porous metal complex is improved by the hydroxy group contained in the porous metal complex used as the template. As a result, the distortion and collapse of the structure of the carbon material during the manufacturing process of the carbon material are suppressed to a minimum, and a stable quality carbon material can be supplied.

It is a figure which shows the diffraction pattern measured with the powder X-ray-diffraction apparatus about the casting_mold | template obtained in Example 1. FIG. The graph “before cleaning” is a diffraction pattern before ethanol cleaning. On the other hand, the graph “after washing” is a diffraction pattern after ethanol washing. It is a figure which shows the diffraction pattern measured with the powder X-ray-diffraction apparatus about the casting_mold | template obtained in the comparative example 1. The graph “before cleaning” is a diffraction pattern before ethanol cleaning. On the other hand, the graph “after washing” is a diffraction pattern after ethanol washing.

  Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. However, the technical scope of the present invention should be determined based on the description of the scope of claims, and is not limited to the following embodiments.

  One embodiment of the present invention has the following chemical formula 1:

Where M is a central metal and R is an organic ligand.
A step of preparing a porous metal complex containing a three-dimensional porous skeleton structure of a metal complex represented by the above as a template (hereinafter also referred to as “first step”), and contacting the porous metal complex with an organic compound A step of forming a coating film of the organic compound on the surface of the porous metal complex (hereinafter also referred to as “second step”), and heating the metal complex having the coating film of the organic compound formed on the surface. And the manufacturing method of a carbon material including the process (henceforth a "3rd process") which superposes | polymerizes and carbonizes the said organic compound is provided. Hereinafter, it demonstrates in detail in order of a process.

[First step]
In the first step, a porous metal complex including a three-dimensional porous skeleton structure of a metal complex is prepared as a template. This porous metal complex includes a three-dimensional porous skeleton structure of the metal complex represented by Chemical Formula 1 described above. Here, the “template” is a name obtained by transferring a three-dimensional porous skeleton structure of a porous metal complex to a carbon material finally obtained.

  In the metal complex represented by Chemical Formula 1, M is a central metal. In one embodiment of the invention, M is a metal selected from the group consisting of trivalent or tetravalent metals. As will be described later, the organic ligand (R) usually occupies divalence by a coordinate bond with the central metal M. And in the metal complex of Chemical Formula 1 mentioned above, since a hydroxyl group (-OH group) couple | bonds with respect to the central metal M in addition to this, M is good in it being a trivalent or more metal. When M is a tetravalent metal, the pores of the three-dimensional porous skeleton structure in the porous metal complex formed by the metal complex of Chemical Formula 1 can be controlled to a relatively small size. In addition, the metal complex is finally separated and removed from the carbon material as described later, but the central metal M contained in the metal complex may remain in the carbon material that is the final product, though a trace amount. For this reason, such a metal can also be employ | adopted as the central metal M of a metal complex with the intention of leaving a desired metal in a carbon material dare. According to such a form, when the obtained carbon material is used for various applications, it is possible to cause the remaining trace amount of metal to exhibit a catalytic action. In this way, a carbon material having a composite performance may be manufactured. And based on the knowledge as described above, the type of the central metal M can be appropriately determined. More specifically, M is preferably a metal selected from the group consisting of Al, Fe, V, Cr, Ga, and In. Such a form is preferable in that a large amount of carbon material is synthesized with high purity, high efficiency, and low cost. In addition, although the central metal M in a metal complex is 1 type normally, depending on the case, if possible, the metal complex containing 2 or more types of central metals M may be used.

  In the metal complex represented by Chemical Formula 1, R is an organic ligand. In one embodiment of the present invention, R is a compound having two or more coordination sites and capable of forming a crosslinked structure by coordinating with atoms or ions of the central metal M. Specific examples of the organic ligand R include, for example, trans-ethylene dicarboxylic acid, benzene dicarboxylic acid (for example, 1,4-benzenedicarboxylic acid), and benzenetricarboxylic acid (for example, 1,3,5-benzenetricarboxylic acid). , Naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, imidazole dicarboxylic acid, triethylenediamine and the like. However, it is not limited only to these forms, Other forms well-known in this technical field can also be employ | adopted similarly. By selecting the kind of the organic ligand used, the pore diameter in the three-dimensional porous skeleton structure of the metal complex can be controlled. For example, the shorter the distance between two carboxy groups or two amino groups in an organic compound, the smaller the pore size in the porous metal complex. In addition, although the organic ligand R in a metal complex is 1 type normally, the metal complex containing 2 or more types of organic ligands R may be used depending on the case.

  The porous metal complex containing the three-dimensional porous skeleton structure of the metal complex represented by the chemical formula 1 used in the production method of this embodiment is porous as the name suggests. There is no particular limitation on the specific form of “porous”. However, it is preferable that the organic compound in contact with the metal complex has pores of a size that can be introduced into the pores of the metal complex in the steps described later. From such a viewpoint, the pore size of the porous metal complex is preferably about 0.4 nm or more.

  In addition, as a specific example of the metal complex used in this embodiment, for example, Al (OH) (EDC) (EDC = trans-ethylenedicarboxylic acid) or Al (OH) (BDC) (BDC = 1,4-benzene) Dicarboxylic acid) and the like. However, it is not limited only to these forms, and other forms can be similarly adopted with reference to the above description and technical common sense.

  Further, the prepared porous metal complex may be subjected to a vacuum drying treatment for about several hours under a temperature condition of about 50 to 250 ° C., preferably 70 to 200 ° C. By performing such a treatment, the coating film can be formed more efficiently by the organic compound in the second step described later.

The porous metal complex described above has a hydroxy group (—OH group). This hydroxy group is considered to contribute to the excellent water resistance of the porous metal complex. Although the complete mechanism is still unclear, it is considered that the presence of a hydroxy group improves the affinity with water and can reversibly adsorb and desorb water. On the other hand, when a porous metal complex having no hydroxy group (for example, one described in Patent Document 1) is contacted with moisture, the original three-dimensional porous skeleton structure may be distorted or collapsed. The present inventor tried to wash a porous metal complex having no hydroxy group with ethanol (containing a very small amount of water) during the study. As a result, it was found that the BET specific surface area of the porous metal complex, which was 2000 m ² / g or more before washing, decreased to 20 m ² / g or less. And even if it performed the drying process after washing | cleaning and the water | moisture content was removed, it was not confirmed that the fall of this specific surface area recovers. From this, it is clear that the three-dimensional skeleton structure of the porous metal complex is distorted or collapsed by the ethanol washing. And as the cause, it was thought that the water | moisture content contained in ethanol might have influenced. On the other hand, such a decrease in specific surface area was not confirmed in the porous metal complex of the present embodiment having a hydroxy group. For this reason, it was considered that the presence of the hydroxy group greatly contributed to the improvement of the water resistance of the porous metal complex.

  There is no restriction | limiting in particular about the acquisition route of the porous metal complex mentioned above. If a commercially available product exists, the product may be used. On the other hand, if possible, the production method of this embodiment can be carried out using a porous metal complex prepared by itself.

As a technique for preparing the porous metal complex itself, for example, the technique described in the literature (F. Millange et al., Chem. Commun., 2002, 822-823) is exemplified. Of course you can refer to it. Here, the method described in the above document will be briefly described. First, a water-soluble salt containing the central metal M (when the central metal M is Cr, for example, Cr ^III (NO ₃ ) ₃ .xH ₂ O) and the above-described organic ligand (for example, 1, 4 -BDC) and a strong acid (essential to obtain a crystalline metal complex; eg hydrogen fluoride) is added to an excess of water and mixed. Next, the reaction system is heated to a temperature of about 180 to 250 ° C. and maintained for several hours to several days while maintaining the pH of the reaction system at a strongly acidic condition of less than 1. In addition, since the reaction proceeds under strongly acidic conditions, it is preferable to use a reaction vessel whose inner surface is lined with an acid-resistant resin such as Teflon (registered trademark).

Subsequently, the solid product obtained above is recovered and purified according to a conventional method (filtration, washing, etc.). In the product obtained at this stage, the compound added as an organic ligand may remain in a free state. For this reason, the product is calcined in a tubular furnace for about several to several tens of hours under a temperature condition (for example, about 250 to 350 ° C.) at which the organic ligand can be removed. The residue of the added compound can be removed. As a result, the metal complex represented by Chemical Formula 1 described above is obtained. For example, when the above-described raw materials are used, a metal complex having a structure of Cr ^III (OH) {O ₂ C—C ₆ H ₄ —CO ₂ } is obtained. Metal complexes having other compositions can also be prepared by themselves with appropriate reference to known knowledge including the above documents.

[Second step]
In the second step, the porous metal complex prepared in the first step is brought into contact with the organic compound. Thereby, a coating film of an organic compound is formed on the surface of the porous metal complex.

  There is no restriction | limiting in particular about the specific form of the "organic compound" used in a 2nd process, It can introduce | transduce inside the pore of a porous metal complex, and it superposes | polymerizes and carbonizes in the polymerization and carbonization process mentioned later. And any compound that can provide a carbon material. By using such an organic compound, a polymer is formed according to the shape of the pores in the pores of the porous metal complex, and subsequently carbonized, so that a porous carbon material having a high specific surface area having pores can be obtained. Obtainable.

  The organic compound is preferably one that can be liquefied or vaporized so that it can be introduced (preferably easily) into the pores of the porous metal complex. As a method for liquefying the organic compound, for example, a method of heating to a temperature higher than the melting point or a method of dissolving in a solvent can be employed. Furthermore, as a method for vaporizing the organic compound, for example, a method of heating to a temperature equal to or higher than the boiling point, a method using a steam atmosphere, or the like can be employed.

  Specific examples of the “organic compound” that satisfies the above-described conditions include furfuryl alcohol, acrylonitrile, vinyl acetate, styrene, butadiene, isoprene, sucrose, and the like. However, it is not limited only to such a form, Other organic compounds can also be employ | adopted similarly.

  In the second step, the porous metal complex prepared above is brought into contact with the organic compound described above. Thereby, a coating film of an organic compound is formed on the surface of the porous metal complex. The porous metal complex usually has a large number of “pores” inside. For this reason, “to form a coating film on the surface of the porous metal complex” in the present application means that a coating film of an organic compound is also formed on the inner surface of each pore present in the porous metal complex. Means that.

  There is no particular limitation on the method for bringing the porous metal complex into contact with the organic compound. For example, in the case of using a liquid organic compound, the porous metal complex is immersed in the organic compound, and the organic compound is dissolved in the complex compound. It suffices to sufficiently penetrate the hole. When a gaseous organic compound is used, the organic compound can be penetrated into the pores of the complex by placing a porous metal complex in the vapor atmosphere of the organic compound. When introducing the organic compound into the pores of the porous metal complex, it is preferable to reduce the pressure of the porous metal complex in advance.

  In the second step, as described above, it is preferable to remove excess organic compound present on the surface of the porous metal complex after contacting the porous metal complex with the organic compound. At this time, the porous metal complex is preferably washed with a lower aliphatic alcohol such as ethanol or methanol. Thereby, the excess organic compound which exists in the surface of a porous metal complex can be removed reliably. The specific form of the cleaning treatment is not particularly limited, and the cleaning conditions can be appropriately set so that a desired amount of the organic compound remains on the surface of the porous metal complex. As described above, the porous metal complex of this embodiment is considered to have excellent water resistance because it has a hydroxy group. Therefore, as described above, an embodiment including the step of washing with a lower aliphatic alcohol (usually containing a trace amount of water) is one of the preferred embodiments in the present invention. However, in the method for producing a carbon material of the present invention, the porous metal complex used as a template is not limited to the cleaning step using such a specific solvent that may come into contact with moisture. From the preparation of the metal complex to the polymerization / carbonization process described later, the metal complex may come into contact with moisture also in other processes than the washing process. As long as there is still a possibility of coming into contact with moisture other than the washing step, the advantage of the method for producing a carbon material of the present invention using a porous metal complex having a hydroxy group as a template also exists. For this reason, although it can be said that embodiment containing the said washing | cleaning process is one of the suitable embodiment in this invention, implementing the said process is not necessarily essential in this invention.

[Third step]
In the third step, the organic compound is polymerized and carbonized by heating the metal complex having a coating film of the organic compound formed on the surface in the second step. Thereby, the carbon material which is a final product is manufactured.

  There is no restriction | limiting in particular about the specific method and its conditions for heating a metal complex. As long as “the polymerization and carbonization of the organic compound” that is the object of this step can be achieved, any technique and heating conditions can be adopted.

  As an example of the form of heating, for example, a method of producing a carbon material by allowing the reaction to proceed in two stages of polymerization and carbonization is exemplified. In such a form, first, heat treatment is performed at a temperature (relatively low temperature) at which the polymerization reaction of the organic compound existing as a coating film on the surface of the metal complex proceeds. Thereby, the polymerization reaction of the organic compound is advanced, and carbonization in the subsequent carbonization step is performed more effectively. In addition, as an example of the heating conditions in the case of a polymerization reaction, conditions, such as heating for about 1 to 48 hours at the temperature of about 60-200 degreeC, are illustrated, for example. In addition, it is preferable that the atmosphere in the case of the heating for polymerization reaction is the atmosphere which vaporized the organic compound which forms the coating film, or inert gas atmosphere (argon, nitrogen, etc.).

  In the above-described embodiment, subsequently, heat treatment is performed at a relatively high temperature in order to advance the carbonization reaction. As a result, the carbonization of the organic compound existing as a polymer proceeds, and the carbon material that is the target product is finally obtained. In order to advance the carbonization reaction, for example, it may be heated at a temperature of about 200 to 1200 ° C., preferably about 500 to 1000 ° C. for about 1 to 48 hours. It is preferable that the atmosphere at the time of heating for advancing the carbonization reaction is an inert gas atmosphere (argon, nitrogen, etc.). In some cases, the product obtained by the carbonization reaction described above is added by bringing hydrocarbons such as propylene into contact with an inert gas as a carrier gas and heating under the same heating conditions as above. Vapor phase carbonization treatment may be performed.

  Through the above steps, a carbon material having a porous structure is obtained. The resulting carbon material has a porous structure in which a three-dimensional porous skeleton structure possessed by the porous metal complex used as a template is transferred. In addition, about the porous metal complex used as a casting_mold | template, the frame | skeleton decomposes | disassembles in the 3rd process mentioned above, and a part of ligand may be concerned with the above-mentioned superposition | polymerization and carbonization. Further, regarding the metal component (mainly, the central metal M) contained in the porous metal complex, those having a low boiling point are vaporized during the carbonization treatment, and therefore no separate removal treatment is necessary. On the other hand, when a metal component can remain in the obtained carbon material, the metal component can be easily dissolved and removed by treatment with an acid. Further, depending on the application, the metal remaining in the obtained carbon material can be used as it is as a catalyst. Further, for the purpose of determining whether or not a certain carbon material belongs to the technical scope of the present invention, the presence of a trace amount of remaining metal component (derived from the central metal M) may be used as an index. .

  As described above, according to the manufacturing method of the present embodiment, distortion and collapse of the structure of the carbon material in the process of manufacturing the carbon material are suppressed to a minimum, and a stable quality carbon material can be supplied. And as the mechanism, it was suggested that the water resistance of the porous metal complex is improved by containing a hydroxy group in the porous metal complex used as a template.

  As described above, the carbon material obtained by the production method of the present embodiment is a result of the porous metal complex used as a template being excellent in water resistance, so that the three-dimensional porous skeleton structure of the complex is accurately reflected. Thus, the transferred three-dimensional structure is obtained. This fact can be quantitatively expressed using the 2θ value of the first peak in the diffraction pattern measured by the powder X-ray diffractometer of the carbon material obtained by the manufacturing method of the present embodiment. That is, the value of 2θ of the first peak in the diffraction pattern of the carbon material measured by a powder X-ray diffractometer is ± 1 with respect to the value of 2θ of the first peak of the porous metal complex used as a template. It is preferably in the range of °, more preferably in the range of ± 0.5 °, and particularly preferably in the range of ± 0.2 °.

  The carbon material obtained by the manufacturing method of the present embodiment can be used for various applications that are conventionally known as applications of carbon materials. For example, the active material can be used in an electrochemical device such as a battery (for example, a lithium ion secondary battery) or a capacitor. It can also be used as a gas storage material for storing high value-added gases such as hydrogen and methane. Even when used in any of these applications, it is preferable that the structure of the obtained carbon material is uniform and stable, particularly when industrial mass production is taken into consideration. In this respect, the manufacturing method of the present embodiment in which the carbon material having a desired structure can be stably manufactured has an advantageous effect over the prior art. In addition, the metal complex used as a template in this embodiment is known as the compound itself (the above-mentioned document (Chem. Commun.)). On the other hand, Patent Document 1 discloses a technique for producing a carbon material by carbonizing an organic compound using a metal complex as a template. However, it is remarkable that even those skilled in the art at the time of filing the present application could not predict that the effects as in the present invention can be obtained when these known facts are combined.

  The effect of this invention is demonstrated using a following example and a comparative example. However, the technical scope of the present invention is not limited only to the following examples.

[Example 1]
Three-dimensional porosity represented by Al (OH) (EDC) (EDC = trans-ethylenedicarboxylic acid) according to the method described in the literature (F. Millange et al., Chem. Commun., 2002, 822-823) A porous metal complex containing a conductive skeleton structure was prepared and used as a template below. Here, FIG. 1 shows a diffraction pattern of the obtained template measured by a powder X-ray diffractometer. “Before cleaning” is the diffraction pattern of the mold at this stage. As shown in FIG. 1, a sharp peak (first peak) was observed in the vicinity of 2θ = 10.4 °. The diffraction pattern measured after washing the prepared template with ethanol is also shown in FIG. “After washing” is a diffraction pattern after washing with ethanol. As shown in FIG. 1, in the porous metal complex prepared as a template in this example, almost the same diffraction pattern as that before the cleaning was observed even after the ethanol cleaning.

The mold prepared above was vacuum dried at 80 ° C. for 3 hours. Thereafter, a sufficient amount of furfuryl alcohol to penetrate into the pores of the mold was added and held with stirring. Next, the template was washed with ethanol to remove excess furfuryl alcohol remaining on the surface of the template (including the surface inside the pores). Thereafter, heat treatment was performed at 150 ° C. to polymerize furfuryl alcohol, and then the polymer was carbonized by heat treatment at 800 ° C. in an argon atmosphere. Furthermore, vapor phase carbonization was performed at 800 ° C. while propylene (carrier gas N ₂ ) was allowed to flow through the reaction tube in a quartz reaction tube to obtain a carbon material.

  The obtained carbon material has a structure in which a three-dimensional porous skeleton structure of a porous metal complex used as a template is transferred. In order to confirm this, when the diffraction pattern of the obtained carbon material was measured with a powder X-ray diffractometer, it was almost the same as shown in FIG. 1 (a sharp peak around 2θ = 10.4 ° (first peak)). A diffraction pattern was observed.

[Example 2]
A carbon material was produced in the same manner as in Example 1 except that the temperature of the heat treatment in an argon atmosphere was 1000 ° C. and no subsequent vapor phase carbonization was performed. When the X-ray diffraction pattern was measured for the obtained carbon material in the same manner as in Example 1, the same result was obtained.

[Example 3]
Carbon was prepared by the same method as in Example 2 except that Al (OH) (BDC) (BDC = 1,4-benzenedicarboxylic acid) was used instead of Al (OH) (EDC) as a template. The material was manufactured.

  When the X-ray diffraction patterns before and after the ethanol cleaning were measured for the above-mentioned template in the same manner as in Example 1, a sharp peak was observed around 2θ = 17.5 ° before and after the cleaning.

  Moreover, when the X-ray-diffraction pattern was similarly measured about the obtained carbon material, the result similar to the above was obtained. For this reason, also in the present Example, it is shown that the obtained carbon material has a structure in which the three-dimensional porous skeleton structure of the porous metal complex used as a template is transferred.

[Comparative Example 1]
With reference to the description of Example 1 of Patent Document 1, Zn ₄ O (BDC) ₃ (BDC = 1,4-benzenedicarboxylic acid) was prepared as a template. Here, FIG. 2 shows a diffraction pattern measured by a powder X-ray diffractometer for the prepared template. “Before cleaning” is the diffraction pattern of the mold at this stage. As shown in FIG. 2, a sharp peak was observed around 2θ = 6.9 °. In addition, the diffraction pattern measured after wash | cleaning the prepared casting_mold | template with ethanol is shown collectively in FIG. “After washing” is a diffraction pattern after washing with ethanol. As shown in FIG. 2, in the porous metal complex prepared as a template in this comparative example, the first peak of the diffraction pattern after ethanol washing is shifted to 2θ = 19.3 °, and the other peaks It can be seen that a large number of cases occurred. From this, it is considered that the porous metal complex of this comparative example is distorted in the three-dimensional porous skeleton structure by ethanol washing, or the structure is collapsed.

Further, the BET specific surface area as measured by N ₂ adsorption on the prepared templates were compared before and after the ethanol wash. As a result, the BET specific surface area, which was about 2300 m ² / g before ethanol washing, decreased to 17 m ² / g after ethanol washing, strongly suggesting that the three-dimensional porous skeleton structure is no longer maintained. It was done.

  On the other hand, using the mold prepared above, a carbon material was manufactured by the same method as in Example 2 described above. When the X-ray diffraction pattern of the obtained carbon material was measured in the same manner as in Example 1, it was almost the same as “after cleaning” shown in FIG. The diffraction pattern of was confirmed. This suggests that the template structure in which the three-dimensional porous skeletal structure is distorted and collapsed due to the influence of moisture such as ethanol washing has been transferred to the carbon material.

[Comparative Example 2]
Except for using Cu ₃ (BTC) ₂ (BTC = 1,3,5-benzenetricarboxylic acid) in place of Zn ₄ O (BDC) ₃ as a template, the same method as in Comparative Example 1 described above, A carbon material was produced.

  When the X-ray diffraction pattern before and after ethanol washing was measured for the above-mentioned template in the same manner as in Comparative Example 1, a sharp peak (first peak) was observed in the vicinity of 2θ = 11.6 ° before washing. After washing, this value shifted to 2θ = 43.3 °, and many other peaks also occurred. From this, it is considered that the porous metal complex of this comparative example is also distorted in the three-dimensional porous skeleton structure by ethanol washing or collapsed.

  On the other hand, the carbon material was manufactured by the method similar to the comparative example 1 mentioned above using the casting_mold | template prepared above. The X-ray diffraction pattern of the obtained carbon material was measured in the same manner as in Example 1. As a result, since it is in contact with moisture by ethanol washing or the like in the manufacturing process, it has a diffraction pattern almost identical to that of the “after washing” described above (having a first peak at 2θ = 43.3 °, and Many other peaks also existed). Therefore, in this comparative example as well, it was confirmed that the template structure in which the three-dimensional porous skeleton structure was distorted and collapsed due to the influence of moisture such as ethanol washing was transferred to the carbon material. It is suggested.

Claims (6)

The following chemical formula 1:
Where M is a central metal and R is an organic ligand.
A first step of preparing, as a template, a porous metal complex containing a three-dimensional porous skeleton structure of a metal complex represented by:
A second step of contacting the porous metal complex with an organic compound to form a coating film of the organic compound on the surface of the porous metal complex;
A third step of heating the metal complex having a coating film of the organic compound formed on a surface thereof to polymerize and carbonize the organic compound;
A method for producing a carbon material, comprising:   The manufacturing method according to claim 1, wherein M is a metal selected from the group consisting of trivalent metals.   The manufacturing method according to claim 2, wherein M is a metal selected from the group consisting of Al, Fe, V, Cr, Ga, and In.   The second step further includes a step of removing excess organic compound by contacting the porous metal complex with an organic compound and then washing the porous metal complex with a lower aliphatic alcohol. Item 4. The method according to any one of Items 1 to 3. A carbon material obtained by the production method according to any one of claims 1 to 4,
Carbon material in which the value of 2θ of the first peak of the carbon material is in a range of ± 1 ° with respect to the value of 2θ of the first peak of the metal complex in the diffraction pattern measured by the powder X-ray diffractometer .   A battery active material comprising the carbon material according to claim 5.